Phenol and thiophenol methylene alkyl ethers



PHENOL AND THIOPHENOL METHYLENE ALKYL ETHERS Gerhard Schrader, Opladen,Germany, assignor to Farbenfabriken Bayer Aktiengesellschaft,Leverkusen, Germany, a corporation of Germany No Drawing. ApplicationMarch 10, 1954 Serial No. 415,443

Claims priority, application Germany March 16, 1953 7 Claims. (Cl.260-609) This invention relates to new insecticides and.,to a

process of making same.

In accordance with the invention it has been found that phenol andthiophenol methylene alkylethers of the general formula where R standsfor an alkyl radical, X is chlorine and X is hydrogen or chlorine, arevery effective insecticides.

The new compounds are easily obtainable from phenols or thiophenolswhich are substituted in the aromatic nucleus by at least one chlorineatom, by condensation with halogeno methyl ethers or halogeno methylthioethers in the presence of acid binding agents. The reaction ispreferably carried out at elevated temperature in a suitable solvent andyields methylene ethers of the above formula even when the phenol or thethiophenol component is applied in excess. This result is mostsurprising since in many reactions of the halogeno methyl ethers inaddition to the halogen atom the ether-group is replaced by othergroups.

The new compounds are liquids which can be distilled at reduced pressurewithout decomposition. They are distinguished by outstandinginsecticidal properties.

The invention is further illustrated by the following examples withoutbeing restricted thereto.

Example 1 49 grams of 2,4-dichlorophenol are dissolved in 200 cc. ofmethyl ethyl ketone. 45 grams of pulverised potassium carbonate areadded to the solution with stirring. 29 grams of chloro methyl ethylether (B. P.: 82-83 C. at a pressure of 760 mm. Hg) are introduced intothe suspension dropwise at 70 C. while continuously stirring. Thetemperature is maintained at 70 C. for another hour and the resultingsalts are filtered off with suction. The solvent is evaporated from thefiltrate in vacuum. The residue is heated to 70 C. at a pressure of 2mm. Hg 15 grams of the new ether of the following formula mQoomoonn B.P.: 107 C. at a pressure of 0.05 mm. Hg are obtained. An 0.1% aqueoussolution of the ether kills plant-lice to 100%.

Example 2 45 grams of 4-chlorothiophenol are dissolved in 350 cc. ofmethyl ethyl ketone. 45 grams of potassium carbonate are added to thesolution which is heated to 70 C. At this temperature 33 grams ofchloromethyl-thioethylether are run in within 30 minutes and thesolution is kept at 70 C. for another hour. After filtering off the2,833,829 Patented May 6, 1958 2 r salts the solvent is distilled ofifrom the filtrate. The residue is kept at 50-60 C. at a pressure of 2mm. Hg 54 grams of the ether having the-formula B. P.: 99-100" C. at apressure of 0.05 mm. Hg are obtained.

Example 3 v v 38.5 grams of 4-chlorophenol are. dissolved in 200 cc.

of methyl ethyl ketone. 45 grams of dried and sifted potassium carbonateare added to the solution into which 33 grams of chloromethyl thioethylether are introduced at C. dropwise with good stirring. I Thetemperature is kept at 70 C. for another hour, the reaction productfiltered with suction andworked up as described in the precedingexample. 50 grams of the ether having the formula oxOoonlsoun B. P.: 137C. at a pressureof 2 mm. Hg are obtained. An 0.01% aqueous solution ofthis compound kills plant-lice safely.

Example 4 B. P.: 107 C. at a pressure of 2 mm. Hg are obtained. An 0.1%solution of this compound kills plant-lice safely to Example 5 50 gramsof 2,4-dichlorophenol are dissolved in 300 cc. of methyl ethyl ketone.45 grams of dried and sifted potassium carbonate are added to thesuspension. At 70 C. 34 grams of chloromethyl thioethyl ether are addeddropwise to the suspension which is kept at 70 C. for a further 30minutes. After working up as described in the preceding examples, 60grams of the ether of the formula (HQ-0.0111. s 02H B. P.: 126 C. at apressureof 0.5 mm. Hg are obtained.

An 0.01% aqueous solution of this ether kills plantlice to 100%.

I claim: I 1. A compound having the formula in which X is chlorine, X isa member selected from the group consisting of hydrogen and chlorine, Ais a member selected from the group consisting of oxygen and sulfur andR is a lower alkyl radical having from 1-4 carbon atoms.

2. A compound having the formula cuOo-om-s-mm 3. A process for theproduction of phenol and thioesam phenol methylene alkyl ethers whichcomprises reacting 5. A compound having the formula 21 chlorophenolhaving the formula 2 1 cl--scmscmn 5 6. A compound having the formula inwhich X is chlorine, X is a member selected from the group consisting ofhydrogen and chlorine with a halogeno methyl alkyl ether having theformula Hill-CHy-A-R 01 10 7. A compound having the formula in which Ais a member selected from the group con- CaHs.O.CH:.S -Cl sisting ofoxygen and sulfur and R is a lower alkyl radical having from 1-4 carbonatoms in the presence References Cited in the fil f this patent of anacid-binding agent. 15

UNITED STATES PATENTS 2,205,392 Coleman et a1. June 25, 1940 or.-O.CH:.0.C:H5 2,352,078 Coleman et a1 June 20, 1944 2,463,541 Houk. Mar.8, 1949 l 20 4. A compound having the formula

1. A COMPOUND HAVING THE FORMULA
 3. A PROCESS FOR THE PRODUCTION OFPHENOL AND THIOPHENOL METHYLENE ALKYL ETHERS WHICH COMPRISES REACTING ACHLOROPHENOL HAVING THE FORMULA